Methods of forming thin metal-containing films by chemical phase deposition

Abstract

Methods of forming thin metal-containing films by chemical phase deposition, particularly atomic layer deposition (ALD) and chemical vapor deposition (CVD), are provided. The methods comprise delivering at least one organometallic precursor to a substrate, wherein the at least one precursor corresponds in structure to Formula (II); wherein: M is Ru, Fe or Os; R is Q-C 10 -alkyl; X is C 1 -C 10 -alkyl; and n is zero, 1, 2, 3, 4 or 5. Further provided are methods of making precursors disclosed herein.

What is claimed is: 
     
       1. A method of forming a metal-containing thin film by atomic layer deposition, the method comprising delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II:
   Cp(R) n M(CO) 2 (X)  (Formula II)
 
 wherein: 
 M is Ru or Os; 
 R is C 1 -C 10 -alkyl; 
 X is C 1 -C 10 -alkyl; 
 n is zero, 1, 2, 3, 4 or 5. 
 
     
     
       2. The method of  claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Ru; 
 R is methyl, ethyl, propyl or butyl; 
 X is methyl, ethyl, propyl or butyl; and 
 n is zero, 1 or 2. 
 
     
     
       3. The method of  claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Ru; 
 R is methyl or ethyl; 
 X is methyl or ethyl; and 
 n is zero or 1. 
 
     
     
       4. The method of  claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Os; 
 R is methyl, ethyl, propyl or butyl; 
 X is methyl, ethyl, propyl or butyl; and 
 n is zero, 1 or 2. 
 
     
     
       5. The method of  claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Os; 
 R is methyl or ethyl; 
 X is methyl or ethyl; and 
 n is zero or 1. 
 
     
     
       6. The method of  claim 1 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:
 (cyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (methylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (ethylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (propylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (butylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (methylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (ethylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (propylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (butylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (methylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (ethylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (propylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (butylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (methylcyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (ethylcyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (propylcyclopentadienyl)osmium(ethyl)(dicarbonyl); and 
 (butylcyclopentadienyl)osmium(ethyl)(dicarbonyl). 
 
     
     
       7. The method of  claim 1 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:
 (cyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(methyl)(dicarbonyl); and 
 (cyclopentadienyl)osmium(ethyl)(dicarbonyl). 
 
     
     
       8. The method of  claim 1 , wherein the at least one precursor corresponding in structure to Formula II is (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl). 
     
     
       9. The method of  claim 1 , wherein the atomic layer deposition is photo-assisted atomic layer deposition. 
     
     
       10. The method of  claim 1 , wherein the atomic layer deposition is liquid injection atomic layer deposition. 
     
     
       11. The method of  claim 1 , further comprising delivering at least one appropriate co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, allylhydrazine, borane, silane, ozone and a combination thereof to the substrate. 
     
     
       12. The method of  claim 1 , wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source. 
     
     
       13. The method of  claim 12 , wherein the oxygen source is selected from H 2 O, O 2  or ozone. 
     
     
       14. The method of  claim 1 , wherein the metal-containing thin film is used for memory and logic applications. 
     
     
       15. A method of forming a metal-containing thin film by chemical vapor deposition, the method comprising delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II:
   Cp(R) n M(CO) 2 (X)  (Formula II)
 
 wherein: 
 M is Ru or Os; 
 R is C 1 -C 10 -alkyl; 
 X is C 1 -C 10 -alkyl; and 
 n is 0, 1, 2, 3, 4 or 5. 
 
     
     
       16. The method of  claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Ru; 
 R is methyl, ethyl, propyl or butyl; 
 X is methyl, ethyl, propyl or butyl; and 
 n is zero, 1 or 2. 
 
     
     
       17. The method of  claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Ru; 
 R is methyl or ethyl; 
 X is methyl or ethyl; and 
 n is zero or 1. 
 
     
     
       18. The method of  claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Os; 
 R is methyl, ethyl, propyl or butyl; 
 X is methyl, ethyl, propyl or butyl; and 
 n is zero, 1 or 2. 
 
     
     
       19. The method of  claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:
 M is Os; 
 R is methyl or ethyl; 
 X is methyl or ethyl; and 
 n is zero or 1. 
 
     
     
       20. The method of  claim 15 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:
 (cyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (methylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (ethylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (propylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (butylcyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (methylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (ethylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (propylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (butylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (methylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (ethylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (propylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (butylcyclopentadienyl)osmium(methyl)(dicarbonyl); 
 (methylcyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (ethylcyclopentadienyl)osmium(ethyl)(dicarbonyl); 
 (propylcyclopentadienyl)osmium(ethyl)(dicarbonyl); and 
 (butylcyclopentadienyl)osmium(ethyl)(dicarbonyl). 
 
     
     
       21. The method of  claim 15 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:
 (cyclopentadienyl)ruthenium(methyl)(dicarbonyl); 
 (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl); 
 (cyclopentadienyl)osmium(methyl)(dicarbonyl); and 
 (cyclopentadienyl)osmium(ethyl)(dicarbonyl). 
 
     
     
       22. The method of  claim 15 , wherein the at least one precursor corresponding in structure to Formula II is (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl). 
     
     
       23. The method of  claim 15 , wherein the chemical vapor deposition is photo-assisted chemical vapor deposition. 
     
     
       24. The method of  claim 15 , wherein the chemical vapor deposition is liquid injection chemical vapor deposition. 
     
     
       25. The method of  claim 15 , further comprising delivering at least one appropriate co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, allylhydrazine, borane, silane, ozone and a combination thereof to the substrate. 
     
     
       26. The method of  claim 15 , wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source. 
     
     
       27. The method of  claim 26 , wherein the oxygen source is selected from H 2 O, O 2  or ozone. 
     
     
       28. The method of  claim 15 , wherein the metal-containing thin film is used for memory and logic applications. 
     
     
       29. A method of preparing a ruthenium precursor of Formula II,
   Cp(R) n M(CO) 2 (X)  (Formula II)
 
 wherein: 
 M is Ru; 
 R is C 1 -C 10 -alkyl; 
 X is C 1 -C 10 -alkyl; and 
 n is zero, 1, 2, 3, 4 or 5, 
 the method comprising:
 reacting Ru 3 (CO) 12  with 3(CpR n )H to yield 3Ru(CpR n )(CO) 2 H and 6CO; 
 reacting Ru(CpR n )(CO) 2 H with BuLi to yield Li[Ru(CpR n )(CO) 2 ] and BuH; 
 and 
 reacting Li[Ru(CpR n )(CO) 2 ] with XBr to yield Ru(CpR n )(CO) 2 X and LiBr.